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Determining degradation kinetics, byproducts and toxicity for the reductive treatment of Nitroguanidine (NQ) by magnesium-based bimetal Mg/Cu
Energetic-laden process water from industrial munition facilities can be treated by zero-valent metals (ZVMs) or zero-valent iron (ZVI) to remove residual energetics. This reduction-based treatment is significantly enhanced with the addition of a secondary catalytic metal (i.e. forming a bimetal rea...
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Published in: | Journal of hazardous materials 2022-02, Vol.423 (Pt A), p.126943-126943, Article 126943 |
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container_end_page | 126943 |
container_issue | Pt A |
container_start_page | 126943 |
container_title | Journal of hazardous materials |
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creator | Mai, A. Hadnagy, E. Abraham, J. Terracciano, A. Zheng, Z. Smolinski, B. Koutsospyros, A. Christodoulatos, C. |
description | Energetic-laden process water from industrial munition facilities can be treated by zero-valent metals (ZVMs) or zero-valent iron (ZVI) to remove residual energetics. This reduction-based treatment is significantly enhanced with the addition of a secondary catalytic metal (i.e. forming a bimetal reagent). The reagent is further enhanced by using a more reductive base metal, such as Mg. In this work, the reductive degradation of nitroguanidine (NQ) in aqueous solutions by Mg/Cu bimetal is investigated. Two initial pH conditions (unadjusted and pH 2.7) were studied. Under unadjusted initial pH conditions, 90% of NQ degraded within 30 min reaction time. After 150 min, NQ degradation generated a suite of products including guanidine (44%), cyanamide (31%), formamide (15%), aminoguanidine (AQ) (6%), urea (2%) and cyanoguanidine (0.03%), leading to 100.0% carbon closure when accounting for residual NQ. The experimentally-derived degradation reaction pathway consisted of two parallel reactions: nitroreduction led to formation of AQ with further degradation to urea, cyanamide and formamide, or reductive cleavage of the N-N bond led to guanidine formation. Toxicological assessments indicated only cyanamide and AQ were toxic to S. obliquus at certain concentrations. A lowered initial pH promoted AQ transformation to benign formamide, thus reducing toxicity and complexity of products.
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•Nitroguanidine (NQ) underwent rapid reductive degradation by a novel Mg-based bimetallic reagent.•Bimetal reagent utilized unconventional metal, Mg, with reduction catalyzed by Cu.•Comprehensive analysis of by- and end-products and a reaction pathway led to complete carbon closure.•Byproduct toxicity was determined with microalgae strain S. obliquus.•Reaction pathway and treated effluent toxicity can be controlled with pH. |
doi_str_mv | 10.1016/j.jhazmat.2021.126943 |
format | article |
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[Display omitted]
•Nitroguanidine (NQ) underwent rapid reductive degradation by a novel Mg-based bimetallic reagent.•Bimetal reagent utilized unconventional metal, Mg, with reduction catalyzed by Cu.•Comprehensive analysis of by- and end-products and a reaction pathway led to complete carbon closure.•Byproduct toxicity was determined with microalgae strain S. obliquus.•Reaction pathway and treated effluent toxicity can be controlled with pH.</description><identifier>ISSN: 0304-3894</identifier><identifier>EISSN: 1873-3336</identifier><identifier>DOI: 10.1016/j.jhazmat.2021.126943</identifier><identifier>PMID: 34481399</identifier><language>eng</language><publisher>Netherlands: Elsevier B.V</publisher><subject>Aquatic toxicity ; Bimetallic ; Byproducts ; Guanidines - toxicity ; Iron ; Kinetics ; Magnesium ; Reductive degradation ; Water Pollutants, Chemical - toxicity</subject><ispartof>Journal of hazardous materials, 2022-02, Vol.423 (Pt A), p.126943-126943, Article 126943</ispartof><rights>2021 Elsevier B.V.</rights><rights>Copyright © 2021 Elsevier B.V. All rights reserved.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c365t-a87cdb29dc6e2cfc0edea13b654f590b14ff10f93dab7c9b3f8fdbfd002977d53</citedby><cites>FETCH-LOGICAL-c365t-a87cdb29dc6e2cfc0edea13b654f590b14ff10f93dab7c9b3f8fdbfd002977d53</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/34481399$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Mai, A.</creatorcontrib><creatorcontrib>Hadnagy, E.</creatorcontrib><creatorcontrib>Abraham, J.</creatorcontrib><creatorcontrib>Terracciano, A.</creatorcontrib><creatorcontrib>Zheng, Z.</creatorcontrib><creatorcontrib>Smolinski, B.</creatorcontrib><creatorcontrib>Koutsospyros, A.</creatorcontrib><creatorcontrib>Christodoulatos, C.</creatorcontrib><title>Determining degradation kinetics, byproducts and toxicity for the reductive treatment of Nitroguanidine (NQ) by magnesium-based bimetal Mg/Cu</title><title>Journal of hazardous materials</title><addtitle>J Hazard Mater</addtitle><description>Energetic-laden process water from industrial munition facilities can be treated by zero-valent metals (ZVMs) or zero-valent iron (ZVI) to remove residual energetics. This reduction-based treatment is significantly enhanced with the addition of a secondary catalytic metal (i.e. forming a bimetal reagent). The reagent is further enhanced by using a more reductive base metal, such as Mg. In this work, the reductive degradation of nitroguanidine (NQ) in aqueous solutions by Mg/Cu bimetal is investigated. Two initial pH conditions (unadjusted and pH 2.7) were studied. Under unadjusted initial pH conditions, 90% of NQ degraded within 30 min reaction time. After 150 min, NQ degradation generated a suite of products including guanidine (44%), cyanamide (31%), formamide (15%), aminoguanidine (AQ) (6%), urea (2%) and cyanoguanidine (0.03%), leading to 100.0% carbon closure when accounting for residual NQ. The experimentally-derived degradation reaction pathway consisted of two parallel reactions: nitroreduction led to formation of AQ with further degradation to urea, cyanamide and formamide, or reductive cleavage of the N-N bond led to guanidine formation. Toxicological assessments indicated only cyanamide and AQ were toxic to S. obliquus at certain concentrations. A lowered initial pH promoted AQ transformation to benign formamide, thus reducing toxicity and complexity of products.
[Display omitted]
•Nitroguanidine (NQ) underwent rapid reductive degradation by a novel Mg-based bimetallic reagent.•Bimetal reagent utilized unconventional metal, Mg, with reduction catalyzed by Cu.•Comprehensive analysis of by- and end-products and a reaction pathway led to complete carbon closure.•Byproduct toxicity was determined with microalgae strain S. obliquus.•Reaction pathway and treated effluent toxicity can be controlled with pH.</description><subject>Aquatic toxicity</subject><subject>Bimetallic</subject><subject>Byproducts</subject><subject>Guanidines - toxicity</subject><subject>Iron</subject><subject>Kinetics</subject><subject>Magnesium</subject><subject>Reductive degradation</subject><subject>Water Pollutants, Chemical - toxicity</subject><issn>0304-3894</issn><issn>1873-3336</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><recordid>eNqFkctuFDEQRS0EIkPgE0BeBome2O1-eYXQ8JRCEBKsLT_KnRqm7cR2Rwz_wD_ToxnYsqpFnXuvqi4hzzlbc8a7y-16e6N_Tbqsa1bzNa872YgHZMWHXlRCiO4hWTHBmkoMsjkjT3LeMsZ43zaPyZlomoELKVfk91sokCYMGEbqYEza6YIx0B8YoKDNr6jZ36boZlsy1cHREn-ixbKnPiZaboAmOCzxHmhJoMsEodDo6TWWFMdZB3SLFb24_vpysaKTHgNknKfK6AyOGpyg6B39PF5u5qfkkde7DM9O85x8f__u2-ZjdfXlw6fNm6vKiq4tlR5660wtne2gtt4ycKC5MF3b-FYywxvvOfNSOG16K43wg3fGO8Zq2feuFefk4ui7XHY3Qy5qwmxht9MB4pxV3XZS9JINckHbI2pTzDmBV7cJJ532ijN1aEJt1akJdWhCHZtYdC9OEbOZwP1T_X39Arw-ArAceo-QVLYIwYLDBLYoF_E_EX8AhPygnQ</recordid><startdate>20220205</startdate><enddate>20220205</enddate><creator>Mai, A.</creator><creator>Hadnagy, E.</creator><creator>Abraham, J.</creator><creator>Terracciano, A.</creator><creator>Zheng, Z.</creator><creator>Smolinski, B.</creator><creator>Koutsospyros, A.</creator><creator>Christodoulatos, C.</creator><general>Elsevier B.V</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20220205</creationdate><title>Determining degradation kinetics, byproducts and toxicity for the reductive treatment of Nitroguanidine (NQ) by magnesium-based bimetal Mg/Cu</title><author>Mai, A. ; Hadnagy, E. ; Abraham, J. ; Terracciano, A. ; Zheng, Z. ; Smolinski, B. ; Koutsospyros, A. ; Christodoulatos, C.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c365t-a87cdb29dc6e2cfc0edea13b654f590b14ff10f93dab7c9b3f8fdbfd002977d53</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><topic>Aquatic toxicity</topic><topic>Bimetallic</topic><topic>Byproducts</topic><topic>Guanidines - toxicity</topic><topic>Iron</topic><topic>Kinetics</topic><topic>Magnesium</topic><topic>Reductive degradation</topic><topic>Water Pollutants, Chemical - toxicity</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Mai, A.</creatorcontrib><creatorcontrib>Hadnagy, E.</creatorcontrib><creatorcontrib>Abraham, J.</creatorcontrib><creatorcontrib>Terracciano, A.</creatorcontrib><creatorcontrib>Zheng, Z.</creatorcontrib><creatorcontrib>Smolinski, B.</creatorcontrib><creatorcontrib>Koutsospyros, A.</creatorcontrib><creatorcontrib>Christodoulatos, C.</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of hazardous materials</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Mai, A.</au><au>Hadnagy, E.</au><au>Abraham, J.</au><au>Terracciano, A.</au><au>Zheng, Z.</au><au>Smolinski, B.</au><au>Koutsospyros, A.</au><au>Christodoulatos, C.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Determining degradation kinetics, byproducts and toxicity for the reductive treatment of Nitroguanidine (NQ) by magnesium-based bimetal Mg/Cu</atitle><jtitle>Journal of hazardous materials</jtitle><addtitle>J Hazard Mater</addtitle><date>2022-02-05</date><risdate>2022</risdate><volume>423</volume><issue>Pt A</issue><spage>126943</spage><epage>126943</epage><pages>126943-126943</pages><artnum>126943</artnum><issn>0304-3894</issn><eissn>1873-3336</eissn><abstract>Energetic-laden process water from industrial munition facilities can be treated by zero-valent metals (ZVMs) or zero-valent iron (ZVI) to remove residual energetics. This reduction-based treatment is significantly enhanced with the addition of a secondary catalytic metal (i.e. forming a bimetal reagent). The reagent is further enhanced by using a more reductive base metal, such as Mg. In this work, the reductive degradation of nitroguanidine (NQ) in aqueous solutions by Mg/Cu bimetal is investigated. Two initial pH conditions (unadjusted and pH 2.7) were studied. Under unadjusted initial pH conditions, 90% of NQ degraded within 30 min reaction time. After 150 min, NQ degradation generated a suite of products including guanidine (44%), cyanamide (31%), formamide (15%), aminoguanidine (AQ) (6%), urea (2%) and cyanoguanidine (0.03%), leading to 100.0% carbon closure when accounting for residual NQ. The experimentally-derived degradation reaction pathway consisted of two parallel reactions: nitroreduction led to formation of AQ with further degradation to urea, cyanamide and formamide, or reductive cleavage of the N-N bond led to guanidine formation. Toxicological assessments indicated only cyanamide and AQ were toxic to S. obliquus at certain concentrations. A lowered initial pH promoted AQ transformation to benign formamide, thus reducing toxicity and complexity of products.
[Display omitted]
•Nitroguanidine (NQ) underwent rapid reductive degradation by a novel Mg-based bimetallic reagent.•Bimetal reagent utilized unconventional metal, Mg, with reduction catalyzed by Cu.•Comprehensive analysis of by- and end-products and a reaction pathway led to complete carbon closure.•Byproduct toxicity was determined with microalgae strain S. obliquus.•Reaction pathway and treated effluent toxicity can be controlled with pH.</abstract><cop>Netherlands</cop><pub>Elsevier B.V</pub><pmid>34481399</pmid><doi>10.1016/j.jhazmat.2021.126943</doi><tpages>1</tpages></addata></record> |
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subjects | Aquatic toxicity Bimetallic Byproducts Guanidines - toxicity Iron Kinetics Magnesium Reductive degradation Water Pollutants, Chemical - toxicity |
title | Determining degradation kinetics, byproducts and toxicity for the reductive treatment of Nitroguanidine (NQ) by magnesium-based bimetal Mg/Cu |
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